CN105617871B - The preparation and its application in emulsion separation of a kind of super infiltration cobaltosic oxide nano pin perforated membrane - Google Patents
The preparation and its application in emulsion separation of a kind of super infiltration cobaltosic oxide nano pin perforated membrane Download PDFInfo
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- CN105617871B CN105617871B CN201510977574.9A CN201510977574A CN105617871B CN 105617871 B CN105617871 B CN 105617871B CN 201510977574 A CN201510977574 A CN 201510977574A CN 105617871 B CN105617871 B CN 105617871B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0205—Separation of non-miscible liquids by gas bubbles or moving solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/028—Microfluidic pore structures
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Abstract
The invention discloses a kind of preparation of super infiltration cobaltosic oxide nano pin perforated membrane and its application in emulsion separation, belong to field of material technology.The present invention is using stainless (steel) wire as substrate, in the hydrothermal precursor solution that will be vertically placed on after its wash clean in polytetrafluoroethyllining lining, hydro-thermal reaction.Finally, the hydro-thermal film calcination processing obtained to hydro-thermal, super hydrophilic, underwater superoleophobic porous super wellability micro-nano compound structure Co is obtained3O4Nanoneedle perforated membrane.Suitable aperture and special profit wellability, the oil droplet in oil-in-water emulsion is set to be blocked on the upside of film and film can not be passed through, it is achieved that the separation of oil-in-water emulsion.In addition, resulting film has good environmental stability, i.e., antiacid, alkali resistant, salt resistance, therefore also achieve and corrosivity emulsion is efficiently separated, there is good application prospect in the sewage disposal of reality.
Description
Technical field
The present invention relates to a kind of super impregnating porous film for oil hydrosol separation and preparation method thereof, and in particular to a kind of
Cobaltosic oxide nano pin perforated membrane with high efficiency oil-water emulsion separating capacity and preparation method thereof, belong to material technology neck
Domain.
Background technology
Probably there are 3,200,000,000 cubic ton oil to enter to form oil-polluted water in water body it is reported that annual, petrochemical industry, household electrical appliances,
The industries such as machine-building, oil refining, machinery, food, medicine, leather, mining, food processing, cleaning metal surface, it is every directly with
Oils contact all contains oil with water.Oily waste water causes huge harm to environment, such as oil floating across the sea, rapidly
Diffuseing to form one layer of air-locked oil film can hinder the reoxygenation of water body to act on, and influence halomereid growth, destroy ocean life
State balances.Particle diameter is that 0.1~20 μm of oil droplet stably is dispersed in water to form oil emulsion, because oil droplet is atomic small, therefore it is single
Pure with settled process is difficult to make water-oil separating.Traditional emulsion separation method has：Fractionation, gravitational separation process, centrifugation
Method, electrically separated method, heating partition method, biological separation method and wetting coarse separation method.But this is usually directed to energy expenditure and two
Secondary pollution.Therefore provide method that is a kind of efficient and being broadly applicable to be used to separate various emulsions, particularly surfactant is steady
Fixed emulsion is particularly important.
Membrane separation technique is a kind of new breaking method, and it realizes demulsification by using the special wellability of material, and
Oil water mixture is separated well.Because its separation equipment is simple, separation process can increasingly automated, applied widely, energy
Consume that low, effect on environment is small, chemical addition agent usage amount is few, high separating efficiency and the advantages that relatively simple operation, big
Had broad application prospects in terms of scale processing oil hydrosol.Jin Jian etc. is by simulating molecule interchain Stagger-wrap in macromolecule
Structure, using CNT as elementary material, wet chemistry method has prepared the nano thickness high intensity with network blackboard
Mesh-structured ultrathin membrane, and use it for the separation (bibliography 1 of oil hydrosol：Shi Z,Zhang W,Zhang F,Liu
X,Wang D,Jin J,et al.Ultrafast separation of emulsified oil/water mixtures by
ultrathin free-standing single-walled carbon nanotube network films.Advanced
materials.2013,25(17):2422.).Feng Lin etc. is prepared for the wire netting of tungsten oxide cladding by the method for Hydrothermal Synthesiss
Separation (bibliography 2 for emulsion：X.Lin,F.Lu,Y.Chen,N.Liu,Y.Cao,L.Xu,Y.Wei L.Feng,One-
step Breaking and Separating Emulsion by Tungsten Oxide Coated Mesh.ACS Appl
Mater Interfaces, 2015,7,8108.) but these films for being used to separate emulsion are not poor mechanical properties, are exactly environment
Stability is poor, i.e., can not be stabilized in the harsh environments such as acid, alkali and salt, therefore in actual applications by certain
Limitation.
The content of the invention
The present invention is resistance to using inorganic material heat endurance, mechanical stability in order to solve problems of the prior art
It corrosion, the advantage such as can repeatedly use, and combine Hydrothermal Synthesiss and method that the later stage calcines is prepared for a kind of having acid and alkali resistance
The stainless steel nethike embrane coated with the cobaltosic oxide nano pin of salt corrosion.This nethike embrane is that one kind has micro-nano multistage composite structure
Multi-hole filtering film, and the Superhydrophilic due to cobaltosic oxide in itself, be provided with nethike embrane super hydrophilic and underwater superoleophobic
Special wellability, and then it is applied to the separation of water serial emulsion and corrosivity emulsion.
The present invention is cut into blockage using stainless (steel) wire as substrate, and successively with acetone, ethanol, HCl/water solution ultrasound
Cleaning, then hydrochloric acid remaining on stainless (steel) wire is rinsed well and dry in an oven with deionized water.By it is cleaned not
Rust steel mesh is vertically placed in the hydrothermal precursor solution in polytetrafluoroethyllining lining, hydro-thermal reaction.Finally, hydro-thermal reaction is obtained
Film calcination processing, obtain super hydrophilic, underwater superoleophobic porous super wellability micro-nano compound structure film, realize a variety of profits breasts
Liquid separation function.Resulting film has good environmental stability, i.e., antiacid, alkali resistant, salt resistance, it is achieved that to corrosivity
Emulsion efficiently separates, and has good actual application value.
The present invention provides a kind of preparation method of super infiltration cobaltosic oxide nano pin perforated membrane, comprises the following steps that：
The first step, clean stainless (steel) wire.Stainless (steel) wire is cut into blockage, it is molten in acetone, ethanol, HCl/water successively respectively
It is cleaned by ultrasonic in liquid, is finally rinsed well hydrochloric acid remaining on stainless (steel) wire with deionized water.In an oven by stainless (steel) wire
Dry stand-by.Described stainless (steel) wire mesh number is 200~1800 mesh.
Second step, configure hydrothermal precursor solution.
Divalence cobalt source, ammonium fluoride (intermediary), alkali compounds are mixed in polytetrafluoro with certain proportioning and deionized water
Stirring obtains hydrothermal precursor solution to dissolving in ethene liner.
The divalence cobalt source is nitric hydrate cobalt (Co (NO3)2·6H2) or cobalt nitrate (Co (NO O3)2) in any one.
The alkali compounds is hexa (HMT), urea (CO (NH2)2) in one kind.
Certain proportioning is:
Divalence cobalt source, ammonium fluoride, urea are with 3:10:The amount proportioning and 50~70mL deionized water mixed dissolutions of 15 materials；
Or,
Divalence cobalt source, ammonium fluoride, hexa are with 5:7:The amount proportioning and 50~70mL deionized waters of 10 materials are mixed
Close dissolving.
3rd step, hydrothermal precursor solution is poured into the reactor with polytetrafluoroethyllining lining, and will washed not
Rust steel mesh is vertically put into hydrothermal precursor solution, obturages reactor, and reactor is moved into baking oven at 90~120 DEG C
6~24h of hydro-thermal reaction, is naturally cooling to room temperature, obtains hydro-thermal film.
Kettle sampling is opened, now the color of stainless (steel) wire is changed into pink colour from original silvery white, and can be seen by microscope
The material pattern for observing pink colour is nanoneedle.
4th step, the hydro-thermal film in Muffle furnace obtained by calcining, the calcining of hydro-thermal film is carried out in air ambient, then it is natural
Room temperature is cooled to, takes out hydro-thermal film.The pink colour that now hydro-thermal film is obtained from hydro-thermal is changed into the Co of black3O4Nanoneedle perforated membrane,
Observe that the pattern of nanoneedle does not change substantially in microscope.
The present invention also provides a kind of application of described super infiltration cobaltosic oxide nano pin perforated membrane, i.e., with gained hydro-thermal
UF membrane oil hydrosol.
Described oil hydrosol is the water system and corrosivity system that dispersed phase size is in 0.1~20 μm, i.e. concentration is little
In the micro-nano emulsion that 1mol/L acid or alkali or saline solution are formed with oil.
The advantage of the invention is that：
(1) the super infiltration porous film preparation of cobaltosic oxide nano pin provided by the invention is simple, for emulsion convenient separation,
Efficiently, fast.
(2) super infiltration cobaltosic oxide nano pin perforated membrane provided by the invention has very strong mechanical property and thermostabilization
Property, had great application prospect in the actual treatment of oil-polluted water.
(3) super infiltration cobaltosic oxide nano pin perforated membrane provided by the invention has very strong environmental stability, Ke Yi
It is used for sewage disposal in harsh soda acid salt environment.
Brief description of the drawings
The scanning electron micrographs of the stainless (steel) wire used in Figure 1A present invention；
Figure 1B is by combining hydro-thermal and calcining the scanning electron micrographs of obtained nanoneedle perforated membrane in the present invention；
The X-ray diffractogram of gained nanoneedle perforated membrane in Fig. 2 present invention；
Fig. 3 A~3E are contact angle schematic diagram of the profit on the nanoneedle perforated membrane that the present invention is prepared.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
The present embodiment is cut into 3.5*3.5cm using 200 mesh stainless (steel) wires as substrate2Blockage, and successively with acetone,
Ethanol, HCl/water solution are cleaned by ultrasonic, and then rinse online remaining hydrochloric acid well with deionized water and dry in an oven.
Washed stainless (steel) wire is vertically placed in the hydrothermal precursor solution in polytetrafluoroethyllining lining, it is anti-to carry out hydro-thermal
Should.Configuring hydrothermal precursor solution is：3mmol Co(NO3)2·6H2O, 10mmol NH4F, 15mmol CO (NH2)2, 70mL goes
Ionized water stirs in polytetrafluoroethyllining lining, then, hydrothermal precursor solution is poured into polytetrafluoroethyllining lining and will washed
Good stainless (steel) wire is vertically put into hydrothermal precursor solution, obturages reactor, and moves it into baking oven the water at 90 DEG C
Thermal response 8h, it is naturally cooling to room temperature and obtains hydro-thermal film.Kettle sampling is opened, finally, the hydro-thermal film in Muffle furnace obtained by calcining, institute
The calcining stated is carried out in air ambient, and heating rate is 1 DEG C/min, and temperature reaches 300 DEG C of holding 3h, then Temperature fall arrives
Room temperature, obtain final products --- super infiltration cobaltosic oxide nano pin perforated membrane.
As Figure 1A and Figure 1B contrasts understand that super to infiltrate on cobaltosic oxide nano pin perforated membrane, nanoneedle is completely covered on
On stainless wire mesh, the hole between twine is set to be less than the dispersed phase in oil hydrosol.Fig. 2 gives gained the super oxidation of infiltration four
The X-ray diffractogram of three cobalt nanoneedle perforated membranes, except those original stainless (steel) wire substrates of expression indicate ■ peak in addition to, it is other
The spinelle Co of all diffraction maximums and standard card3O4(JCPDS 43-1003) is matched completely.Fig. 3 A and Fig. 3 B sets forth
Water and the underwater oily contact angle schematic diagram in the super infiltration cobaltosic oxide nano pin porous film surface, can be obtained, institute from figure
The super infiltration cobaltosic oxide nano pin perforated membrane obtained has super hydrophilic and underwater superoleophobic super wellability, plus the super leaching of gained
The aperture less than emulsion dispersion phase size that profit cobaltosic oxide nano pin perforated membrane has, aoxidizes the super infiltration four of the present invention
Three cobalt nanoneedle perforated membranes can be applied to the separation of oil-in-water emulsion.Oily (gasoline, hexamethylene, isooctane, petroleum ether or diformazan
Benzene) with deionized water by volume 1:100 mixing ultrasounds 1 hour, obtain oil-in-water emulsion.With the super infiltration cobaltosic oxide
Nanoneedle perforated membrane separates under 5kPa negative pressure, and flow velocity is 1600~2000Lm-2H, separative efficiency are more than 99%.It is described
Separative efficiency refer to quality hundred of the oily content after emulsion separation in filtrate compared to the reduction of content oily before emulsion separation
Fraction.
Embodiment 2
Using 300 mesh stainless (steel) wires as substrate, 3.5*3.5cm is cut into2Blockage, and successively with acetone, ethanol,
HCl/water solution is cleaned by ultrasonic 1h, then rinses online remaining hydrochloric acid well with deionized water and dries in an oven.
Washed stainless (steel) wire is vertically placed in the hydrothermal precursor solution in polytetrafluoroethyllining lining, hydro-thermal reaction.
Configure hydrothermal precursor solution：5mmol Co(NO3)2·6H2O, 7mmol NH4F, 10mmol HMT, 50mL deionized water are in poly-
In tetrafluoroethene liner, 1h is stirred, then, hydrothermal precursor solution is poured into polytetrafluoroethyllining lining and stainless by what is washed
Steel mesh is vertically put into hydrothermal precursor solution, obturages reactor, and moves it into baking oven the hydro-thermal reaction at 95 DEG C
24h, it is naturally cooling to room temperature and obtains hydro-thermal film.Kettle sampling is opened, finally, the hydro-thermal film in Muffle furnace obtained by calcining, nethike embrane
Calcining is carried out in air ambient, and heating rate is 1 DEG C/min, and temperature reaches 300 DEG C of holding 3h, then Temperature fall is to room
Temperature, nethike embrane is taken out, super infiltration cobaltosic oxide nano pin perforated membrane as manufactured in the present embodiment.
In described super infiltration cobaltosic oxide nano pin perforated membrane, nanoneedle is completely covered on stainless wire mesh, is made
Hole between twine is less than the dispersed phase in oil hydrosol.Fig. 3 C sets forth underwater oil in the super oxidation of infiltration four three of gained
The contact angle schematic diagram of cobalt nanoneedle porous film surface, can be obtained from figure, and the super infiltration cobaltosic oxide nano pin of gained is porous
Film has super hydrophilic and underwater superoleophobic super wellability, and gained cobaltosic oxide nano pin perforated membrane has necessarily antiacid
Property, the super infiltration cobaltosic oxide nano pin perforated membrane of the present invention is can be applied to the separation of acid oil-in-water emulsion.Oil (gasoline,
Hexamethylene, isooctane, petroleum ether or dimethylbenzene) with the 1mol/LHCl aqueous solution by volume 1:100 mixing ultrasounds 1 hour, are obtained
Acid oil-in-water emulsion.Separated with the super infiltration cobaltosic oxide nano pin perforated membrane of gained under 5kPa negative pressure, flow velocity is
1600~2000Lm-2H, separative efficiency are more than 99%.
Embodiment 3
Using 1000 mesh stainless (steel) wires as substrate, 3.5*3.5cm is cut into2Blockage, and successively with acetone, ethanol,
HCl/water solution is cleaned by ultrasonic 1h, then rinses online remaining hydrochloric acid well with deionized water and dries in an oven.
Washed stainless (steel) wire is vertically placed in the hydrothermal precursor solution in polytetrafluoroethyllining lining, hydro-thermal reaction.
Configure hydrothermal precursor solution：5mmol Co(NO3)2·6H2O, 7mmol NH4F, 10mmol HMT, 60mL deionized water are in poly-
In tetrafluoroethene liner, 1h is stirred, then, hydrothermal precursor solution is poured into polytetrafluoroethyllining lining and stainless by what is washed
Steel mesh is vertically put into hydrothermal precursor solution, obturages reactor, and moves it into baking oven the hydro-thermal reaction at 95 DEG C
12h, it is naturally cooling to room temperature.Kettle sampling is opened, finally, the hydro-thermal film in Muffle furnace obtained by calcining, the calcining of nethike embrane is in sky
Carried out in compression ring border, heating rate is 1 DEG C/min, and temperature reaches 300 DEG C of holding 3h, then Temperature fall takes out nethike embrane to room temperature.
The above-mentioned super infiltration cobaltosic oxide nano pin perforated membrane being prepared, nanoneedle are completely covered on stainless wire mesh, make net
Hole between silk is less than the dispersed phase in oil hydrosol.Fig. 3 D give underwater oil in the super infiltration cobaltosic oxide nano of gained
The contact angle picture of pin porous film surface, can be obtained from figure, and the nanoneedle perforated membrane of gained has super hydrophilic and underwater superoleophobic
Super wellability, and gained cobaltosic oxide nano pin perforated membrane has certain alkali resistance, makes the super oxidation of infiltration four of the present invention
Three cobalt nanoneedle perforated membranes can be applied to the separation of alkaline oil-in-water emulsion.Oily (gasoline, hexamethylene, isooctane, petroleum ether or two
Toluene) with the 1mol/LNaOH aqueous solution by volume 1:100 mixing ultrasounds 1 hour, obtain alkaline oil-in-water emulsion.With gained four
Co 3 O nanoneedle perforated membrane separates under 5kPa negative pressure, and flow velocity is 1600~2000Lm-2H, separative efficiency are more than
99%.
Embodiment 4.
Using 1800 mesh stainless (steel) wires as substrate, 3.5*3.5cm is cut into2Blockage, and successively with acetone, ethanol,
HCl/water solution is cleaned by ultrasonic 1h, then rinses online remaining hydrochloric acid well with deionized water and dries in an oven.
Washed stainless (steel) wire is vertically placed in the hydrothermal precursor solution in polytetrafluoroethyllining lining, hydro-thermal reaction.
Configure hydrothermal precursor solution：3mmol Co(NO3)2·6H2O, 10mmol NH4F, 15mmol CO (NH2)2, 60mL deionizations
Water stirs 1h in polytetrafluoroethyllining lining, then, hydrothermal precursor solution is poured into polytetrafluoroethyllining lining and will washed
Stainless (steel) wire be vertically put into hydrothermal precursor solution, obturage reactor, and move it into baking oven the hydro-thermal at 120 DEG C
6h is reacted, is naturally cooling to room temperature.Open kettle sampling, finally, the hydro-thermal film in Muffle furnace obtained by calcining, the calcining of nethike embrane be
Carried out in air ambient, heating rate is 1 DEG C/min, and temperature reaches 300 DEG C of holding 3h, then Temperature fall takes out net to room temperature
Film, obtain super infiltration cobaltosic oxide nano pin perforated membrane.The above-mentioned super infiltration cobaltosic oxide nano pin that is prepared is porous
Film, nanoneedle are completely covered on stainless wire mesh, the hole between twine is less than the dispersed phase in oil hydrosol.Fig. 3 E give
The underwater oily contact angle picture in gained nanometer wire surface is gone out, can have been obtained from figure, the nanoneedle perforated membrane of gained is with super close
Water and underwater superoleophobic super wellability, and gained cobaltosic oxide nano pin perforated membrane has certain salt-resistance, makes this hair
Bright super infiltration cobaltosic oxide nano pin perforated membrane can be applied to the separation of the oil-in-water emulsion containing high salt concentration.Oil (gasoline,
Hexamethylene, isooctane, petroleum ether or dimethylbenzene) with the 1mol/L NaCl aqueous solution by volume 1:100 mixing ultrasounds 1 hour, are obtained
To the oil-in-water emulsion containing high salt concentration.Divided with the super infiltration cobaltosic oxide nano pin perforated membrane of gained under 5kPa negative pressure
From flow velocity is 1600~2000Lm-2H, separative efficiency are more than 99%.
Claims (8)
- A kind of 1. preparation method of super infiltration cobaltosic oxide nano pin perforated membrane, it is characterised in that：Comprise the following steps that,The first step, clean stainless (steel) wire；Second step, configure hydrothermal precursor solution；Divalence cobalt source, ammonium fluoride, alkali compounds and deionized water are mixed in into stirring in polytetrafluoroethyllining lining, to dissolving, to obtain To hydrothermal precursor solution；3rd step, hydrothermal precursor solution is poured into the reactor with polytetrafluoroethyllining lining, and the stainless steel that will be washed Net is vertically put into hydrothermal precursor solution, obturages reactor, and reactor is moved into baking oven into the hydro-thermal at 90 ~ 120 DEG C 6 ~ 24 h are reacted, room temperature is naturally cooling to, obtains hydro-thermal film；4th step, the hydro-thermal film in Muffle furnace obtained by calcining, the calcining of hydro-thermal film, then Temperature fall are carried out in air ambient To room temperature, hydro-thermal film is taken out, now hydro-thermal film is the Co of black3O4Nanoneedle perforated membrane.
- 2. a kind of preparation method of super infiltration cobaltosic oxide nano pin perforated membrane according to claim 1, its feature exist In：The first step specifically,Stainless (steel) wire is cut into blockage, is cleaned by ultrasonic successively in acetone, ethanol, HCl/water solution respectively, finally uses deionization Water rinses hydrochloric acid remaining on stainless (steel) wire well, in an oven dries stainless (steel) wire stand-by.
- 3. a kind of preparation method of super infiltration cobaltosic oxide nano pin perforated membrane according to claim 1, its feature exist In：Described stainless (steel) wire mesh number is 200 ~ 1800 mesh.
- 4. a kind of preparation method of super infiltration cobaltosic oxide nano pin perforated membrane according to claim 1, its feature exist In：Described divalence cobalt source is nitric hydrate cobalt Co (NO3)2·6H2O or cobalt nitrate Co (NO3)2In any one；The alkali Property compound be one kind in hexa or urea.
- 5. a kind of preparation method of super infiltration cobaltosic oxide nano pin perforated membrane according to claim 1, its feature exist In：Divalence cobalt source, ammonium fluoride and urea are with 3:10:The amount proportioning and 50 ~ 70mL deionized water mixed dissolutions of 15 materials obtain water Hot precursor solution；Or, divalence cobalt source, ammonium fluoride and hexa are with 5:7:The amount proportioning of 10 materials and 50 ~ 70mL are gone Ionized water mixed dissolution obtains hydrothermal precursor solution.
- 6. a kind of preparation method of super infiltration cobaltosic oxide nano pin perforated membrane according to claim 1, its feature exist In：Described calcining is carried out in air ambient, and heating rate is 1 DEG C/min, and temperature reaches 300 DEG C of 3 h of holding.
- A kind of 7. application of super infiltration cobaltosic oxide nano pin perforated membrane, it is characterised in that：It is prepared in claim 1 Nanoneedle perforated membrane oil-water separation emulsion；Described oil hydrosol is water system and the corrosion that dispersed phase size is in 0.1 ~ 20 μm Property system.
- A kind of 8. application of super infiltration cobaltosic oxide nano pin perforated membrane according to claim 7, it is characterised in that：Institute The water system and corrosivity system stated are the micro-nano emulsions that acid of the concentration no more than 1 mol/L or alkali or saline solution are formed with oil.
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| CN106731012B (en) * | 2016-12-22 | 2018-11-27 | 北京航空航天大学 | A kind of super preparation for infiltrating titanium dioxide nano-rod perforated membrane and its application in lotion separation |
| CN108970418B (en) * | 2018-06-25 | 2020-11-27 | 太原科技大学 | Preparation method of super-hydrophilic underwater super-oleophobic oil-water separation net |
| CN109046044B (en) * | 2018-09-10 | 2020-09-08 | 苏州大学 | Composite multilayer network film based on sodium titanate nanowires and cobaltosic oxide nanoneedles as well as preparation method and application thereof |
| CN109292942B (en) * | 2018-09-28 | 2021-08-03 | 江苏大学 | Cobalt oxide/SiO2Preparation method and application of composite net film |
| CN109250789B (en) * | 2018-09-28 | 2021-11-23 | 江苏大学 | Preparation method and application of graphene oxide/cobalt oxide composite net film |
| CN112494997B (en) * | 2020-10-23 | 2022-03-25 | 浙江海洋大学 | Porous super-hydrophilic oleophobic material |
| CN113144917B (en) * | 2021-04-23 | 2022-07-22 | 西南石油大学 | Sea urchin-shaped nickel-cobalt hydrotalcite stainless steel net film and preparation method and application thereof |
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| CN102974226A (en) * | 2012-11-05 | 2013-03-20 | 清华大学 | Super-hydrophilic and underwater super-oleophobic oil-water separation mesh membrane having, and its preparation method |
| CN104548667A (en) * | 2014-12-29 | 2015-04-29 | 清华大学 | Net film applied to oil-in-water emulsion separation, preparation method and application of net film |
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| CN102974226A (en) * | 2012-11-05 | 2013-03-20 | 清华大学 | Super-hydrophilic and underwater super-oleophobic oil-water separation mesh membrane having, and its preparation method |
| CN104548667A (en) * | 2014-12-29 | 2015-04-29 | 清华大学 | Net film applied to oil-in-water emulsion separation, preparation method and application of net film |
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